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Thermochemical kinetics of nitrogen compounds. V. The unimolecular thermal decomposition of diallylamine in the gas phase
Author(s) -
Egger Kurt W.,
Vitins Peter
Publication year - 1974
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550060307
Subject(s) - chemistry , methylamine , arrhenius equation , thermal decomposition , reaction rate constant , torr , kinetics , decomposition , reaction mechanism , activation energy , atmospheric temperature range , elementary reaction , chemical kinetics , thermodynamics , catalysis , organic chemistry , physics , quantum mechanics
Abstract The kinetics of the thermal decomposition of diallylamine to propylene and prop‐2‐enaldimine have been studied in the gas phase in presence of an excess of methylamine over the temperature range of 532.7 to 615.6°K, using a static reaction system. Methylamine reacted with the unstable primary product prop‐2‐enaldimine, forming the thermally stable N ‐methyl prop‐2‐enaldimine. First‐order rate constants, based on the internal standard technique, fit the Arrhenius relationship log k (s −1 ) = (11.04 ± 0.13) − (37.11 ± 0.33 kcal/mole)/2.303 RT. They were independent on the initial total pressure (46–340 torr), the initial pressure of diallylamine (9.2–65 torr), or methylamine as well as the conversion attained. Despite an apparent surface sensitivity, the reaction is essentially homogeneous in nature as demonstrated by experiments carried out in a packed reaction vessel. The observed activation parameters for the title reaction together with those observed earlier for triallylamine and allylcyclohexylamine are consistent with the proposed concerted reaction mechanism involving a cyclic 6‐center transition state. The observed substituent effects suggest a nonsynchronous mode of bond breaking and bond formation.